Polyaldehyde/polyacetal compositions

ABSTRACT

Water-soluble monomers and water-soluble polymers derived therefrom are disclosed. These materials can be used with other vinyl monomers to form water-soluble polymers which are reactive with cellulosic substrates to obtain drastically improved strength, particularly when applied in paper manufacture. The polymers contain at least two mole percent of a monomer represented by the chemical structure: ##STR1## wherein R is H, CH 3 , or C 2  H 5  ; and 
     A is O, or N(R 1 ); and 
     B is CH 2 , CH 2  CH 2  O, ##STR2##  and D is ##STR3## and wherein R 1  is H, CH 3 , C 2  H 5 , (CH 2  CH 2  O) n  H, or (B) q  D, and wherein q is from 1-6, except when B contains nitrogen in which case q is always one; and wherein R 2  is H, CH 3 , C 2  H 5 , or (CH 2  CH 2  O) n  H; and wherein R 4  and R 5  may be the same or different and are, for each individual occurrence, H, CH 3 , C 2  H 5  ; and wherein Z is from the group Cl, Br, I, NO 3 , SO 4  and the like; and wherein m ranges from 0-6; and wherein n is from 1-6.

This is a division of application Ser. No. 625,421 filed June 28, 1984,issued as U.S. Pat. No. 4,508,594 on Apr. 2, 1985.

INTRODUCTION

The present invention relates to new hydrophilic, water-soluble ordispersible vinyl polymers which, when dissolved in water and reactedwith cellulosic fibrous materials, combine with these cellulosicmaterials to form a paper composition having greatly improved strengthproperties.

Three types of paper strength are significantly improved:

1. Wet Web Strength, which is the strength of never-been-dried paper inthe range of about 20-60% solids content (balance is water). Thisproperty is particularly important as it relates to the reliable runningof a paper machine.

2. Wet Strength (or "Rewetted Strength"), which is the strength of paperwhich has been fully dried which is then rewetted by water and thestrength determined. This is differentiated from wet web strength inthat opportunity for curing reactions has occured in the hot dryersection of a paper machine. This curing is frequently necessary for wetstrength resins to achieve their performance.

3. Dry strength, which is the strength of the final dry paper.

The water-soluble polymers of this invention have the property ofimparting improved strength to paper sheet by a combination of thesepolymers which cellulosic fibers making up the paper sheet to form a newcomposition of matter which is a paper sheet composition having improveddry strength and improved wet strength and improved wet web strength andcomprising cellulosic fibers combined with a water-soluble polymer whichcontains at least 2 mole percent of a monomer represented by thechemical structure: ##STR4## wherein R is --H, --CH₃, or --C₂ H₅ ; and

A is O, or N(R₁); and

B is CH₂, CH₂ CH₂ O, ##STR5## and D is ##STR6## and wherein R₁ is --H,--CH₃, --C₂ H₅, (CH₂ CH₂ O)_(n) H, or (B)_(q) D, and wherein q is from1-6, except when B contains nitrogen in which case q is always one; andwherein R₂ is --H, --CH₃, --C₂ H₅, or (CH₂ CH₂ O)_(n) H; and wherein R₃is ##STR7## and wherein R₄ and R₅ may be the same or different and are,for each individual occurance, --H, --CH₃, or --C₂ H₅ ; and wherein Z isfrom the group Cl, Br, I, NO₃, SO₄ and the like; and wherein m rangesfrom 0-6; and wherein n is from 1-6.

Where we use R₃ as ##STR8## we mean to include cyclic acetals such as:##STR9## wherein each individual occurence of R₄ and R₅ may be from thegroup --H, --CH₃, and --C₂ H₅. In this way, cyclic structures such as:##STR10## are included in our invention.

It is, therefore, an object of this invention that new vinyl monomers besynthesized having free aldehyde, acetal, or hemiacetal structureswhich, when reacted with similar monomers or copolymerized with othermonomers, form water-soluble polymers which, when combined withcellulosic fibers, form an improved paper sheet having improved wetstrength properties.

It is another object of this invention to provide for the synthesis ofnew compositions of water-soluble polymers containing reactive aldehyde,acetal, or hemiacetal functionality having the capability to react withcellulosic substrates to improve wet web strength, wet strength, drystrength, and other properties.

It is another object of this invention to provide methods and techniquesfor forming the polymers of this invention which, when combined withcellulosic fibers, achieve the improved strength properties cited above.

It is also an object of this invention to provide the types of polymerswhich can form improved paper sheet having strength propertiesheretofore not found in the art.

Finally, it is an object of this invention to form an improved papersheet having strength properties exceeding any strength found in theart. And, it is an object of this invention to allow the manufacturer ofpaper sheet products to achieve higher manufacturing rates, lower costsper manufactured ton of paper, and higher quality paper products withless discard due to paper tearing in the manufacturing process becauseof the new paper compositions of this invention.

PRIOR ART

Ionic water-soluble polymers often have the property of imparting wetstrength to paper and are especially important in the papermaking artbecause wet strength property allows for improved paper sheet making,faster manufacturing rates, and higher quality paper sheet products.U.S. Pat. Nos. 2,345,543, 2,582,840, 2,596,014, and 3,556,932 are just afew of the patents covering the attempts various parties have made tosolve the problem presented by paper which is not treated to improve itswet strength properties. U.S. Pat. Nos. 3,556,932 particularly pointsout an improvement which is the discovery that ionic water-soluble vinylamide polymers which have been made thermosetting by reason of reactedglyoxal possess beneficial properties to form wet strength agents in themanufacture of paper sheet. It is claimed in this patent that the ionicwater-soluble vinyl amide polymers reacted with glyoxal arethermosetting and cure rapidly at neutral pH's to impart excellent wetstrength to the paper sheet formed in the presence of this reactedpolymer. The polymers are also taught to impart improved dry strength inaddition to the more important wet strength properties. The polymers ofthis U.S. Pat. No. 3,556,932, which is incorporated herein by reference,can be prepared in either cationic or anionic form where the cationicpolymers are self-substantive to the cellulosic fiber when contactedwith said fibers in aqueous suspension. It is taught that the anionicpolymers can be deposited on the cellulosic fibers with the aid of alum,a technique known in the art.

However, the polymers of this reference are the combination ofwater-soluble polyvinyl amides with glyoxal which form a substituted,possibly crosslinked system, which is found to be thermosetting andprovides the improved wet strength. This admixture is subject tochemical equilibrium which can cause difficulties in product stabilityif the admixture is not used appropriately.

U.S. Pat. No. 4,448,908, Pauly et. al., teaches a latex reactive with abiologically active substance forming a conjugate suitable forserological or immunological assay procedures where the latex contains apolymer core and a shell thereover, the shell comprises awater-insoluble monomer of the formula: ##STR11##

These monomers are used in this invention to achieve stability ofimmunologically active materials. This use is considerably differentfrom the use anticipated in the instant invention.

The polymers of the instant invention do not have this drawback and canbe stored for long periods in a form which is less reactive and thensubsequently used as desired to obtain the improved strength for papersheet. The polymers of this invention may be ionic in nature or they maybe neutral and still perform their function. However, because cationicpolymers are self-substantive to the cellulosic fiber, it is preferredthat the water-soluble polymer used in this invention be a polymer whichhas incorporated therein some degree of cationic character. An advantageto using some of the monomers of this invention to form thewater-soluble polymers of this invention which are used to manufacturethe improved strength paper sheet of this invention is that the monomersand, hence, the polymers formed therefrom will contain aldehyde, acetal,or hemiacetal substantive functionality and may also contain cationic oranionic functionality.

In addition, a reference appearing in the journal, Polymer, Sept., 1974,Vol. 15, authored by R. Epton, et al., teaches the formation ofwater-insoluble crosslinked poly(acrylolylaminoacetaldehyde dimethylacetal) and derived urease conjugates. These water-insoluble polymersare hydrolyzed leading to polyaldehydrol gels which were subsequentlyused to immobilize urease enzymes. These immobilized urease enzymematerials demonstrated greater stability during continuous use incolumns, in storage and aqueous buffer suspensions, and to removal ofsubstrate and to temperature changes. The synthesis of thesewater-insoluble gels, the mode of binding enzymes, and the mechanism ofsubstrate inhibition for the polyaldehydrol-urease conjugates arediscussed in this paper.

The polymers of the instant invention are water-soluble and are usedafter hydrolysis to form reactive materials which can be combined withcellulosic fibers to improve strength on a paper sheet. The teachings ofEpton, et al., which are incorporated by reference herein, do notanticipate the teachings of this invention.

THE INVENTION

Our invention is a vinyl monomer capable of being polymerized by freeradical or other initiators and represented by the chemical structure:(After vinyl polymerization) ##STR12## wherein R is --H, --CH₃, or --C₂H₅ ; and

A is O, or N(R₁); and

B is CH₂, CH₂ CH₂ O, ##STR13## and D is ##STR14## and wherein R₁ is --H,--CH₃, --C₂ H₅, (CH₂ CH₂ O)_(n) H, or (B)_(n) D, and wherein q is from1-6, except when B contains nitrogen in which case q is always one; andwherein R₂ is --H, --CH₃, --C₂ H₅, or (CH₂ CH₂ O)_(n) H; and wherein R₃is ##STR15## and wherein R₄ and R₅ may be the same or different and arefor each individual occurence, --H, --CH₃, or --C₂ H₅ ; and wherein Z isfrom the group Cl, Br, I, NO₃, SO₄ and the like; and wherein m rangesfrom 0-6; and wherein n is from 1-6.

As can be seen above, the monomers of this invention are eithersubstituted esters or substituted amides of acrylic, methacrylic orethacrylic acid or acrylamide, methacrylamide, or ethacrylamide. Themonomers contain an aldehyde, acetal, or hemiacetal, depending upon thestate in which the monomer is found or the chemical environment in whichthe monomer is found. In addition, these monomers may contain oleophiliccharacter of varying degree, or cationic character of varying degree.When the nitrogen compound which may be found in the --(B)_(q) D--substitution is quaternized, the material is strongly cationic andcarries with it a gegenion which is chosen from the group consisting ofchloride, bromide, iodide, methyl sulfate and the like. This gegenionmay be changed by ion exchange techniques known in the art to providesalts such as nitrate, sulfate, phosphate, and the like.

There are several synthetic techniques that are available to form thevinyl monomers of this invention. One technique is to react a vinylmonomer acid halide with a substituted amino or alcohol compound whichcontains an acetal group in the following reactions: ##STR16## whereZ=Cl, Br, I, and B,q, R, R₄ and R₅ have their previous meaning.

Other chemical reactions may also be used to synthesize the monomers ofthe instant invention. For example, an article appearing in Tetrahedron,Vol. 29, pages 2947-51 (1973), which is incorporated herein byreference, teaches the N-alkylation of nitriles as a general synthesisof substituted amidines. This reference applies nitrilium salt chemistryto the preparation of amidines which, by analogue, may be applied to thepreparation of substituted acrylamide monomer using the followingreaction sequence: ##STR17## where R' may be ##STR18## and the like, andwhere R₃, R₄ and R₅ have the same meaning as above and where Z=Cl, Br,I, and n is 1-6.

If other substantive functionality is desired in the monomers, they maybe obtained by providing them originally in the acetal form above or inthe R' group in the second sequence of reactions.

However, another sequence of reactions may be available to formcompounds which are reactive, when synthesized as polymeric materials,with cellulosic fibers to improve paper strength. For example, thereaction sequence: ##STR19## and where all other symbols have theirabove stated meanings, should yield reactive monomers which havecationic charge internally as well as the aldehyde, acetal, orhemiacetal structures.

The monomers found to be most useful are those in which

R is H or --CH₃,

A is --O-- or ##STR20## B is --CH₂ --, ##STR21## and D is ##STR22##wherein the designations for R₁, R₂, R₃, m, n, Z, R₄, and R₅ are thesame as above.

The most preferred vinyl monomers used to synthesize the water-solublepolymers of this invention are represented by the structures abovewhere:

R is H or --CH₃,

A is --O-- or --NH--

B is --CH₂ --, and

D is ##STR23## wherein R₄ and R₅ may be the same or different and may beeach individually chosen from the group consisting of H, --CH₃, or 'C₂H₅ ; and R₃ is ##STR24## m is 0-2, and where n is from 1-3.

The Water-Soluble Polymers

To obtain the improved strength on paper of this invention, the monomersdescribed above must be polymerized to obtain a water-soluble polymerwhich contains at least 2 mole percent of the monomers representedabove. Preferably, the water-soluble polymers contain at least 10 molepercent of the above represented monomers and, most preferably, thewater-soluble polymers contain at least 50 mole percent of the monomersrepresented by the chemical structures above. These water-solublepolymers may be synthesized by free radical initiation of the vinylmonomers listed above. Such a free radical initiation may beaccomplished using any free radical initiator known in the art, such asorganic peroxides, Vazo compounds, and/or Redox free radical initiators.These catalysts are well known in the art. In addition, these polymersmay be synthesized as solution polymers in aqueous media, or they may besynthesized in non-aqueous media when such is necessary to obtainpolymers, for example, when copolymerizing with maleic anhydride.Finally, these polymers may be synthesized using water-in-oil emulsionpolymerization techniques as taught in U.S. Pat. No. Re. 28,474, U.S.Pat. No. 28,576, and U.S. Pat. No. 3,284,393, all of which areincorporated herein by reference.

The polymers of the instant invention are formed using the monomersdescribed above, are water-soluble, and may be combined with cellulosicfibers to form an improved paper sheet with strength characteristicsthat to date has been unattainable.

The water-soluble polymers of this invention contain at least 2 molepercent of a monomer represented by the chemical structure: ##STR25##wherein R is --H, --CH₃, or --C₂ H₅ ; and

A is O, or N(R₁); and

B is CH₂, CH₂ CH₂ O, ##STR26## and D is ##STR27## and wherein R₁ is --H,--CH₃, --C₂ H₅, (CH₂ CH₂ O)_(n) H, or (B)_(q) D, and wherein q is from1-6, except when B contains nitrogen in which case q is always one; andwherein R₂ is --H, --CH₃, --C₂ H₅, or (CH₂ CH₂ O)_(n) H; and wherein R₃is ##STR28## and wherein R₄ and R₅ may be the same or different and are,for each individual occurance, --H, --CH₃, or --C₂ H₅ ; and wherein Z isfrom the group Cl, Br, I, NO₃, SO₄ and the like; and wherein m rangesfrom 0-6; and wherein n is from 1-6.

Where we use R₃ as ##STR29## we mean to include cyclic acetals such as:##STR30## wherein each R₄ and R₅ are individually chosen from --H, --CH₃or --C₂ H₅.

The preferred water-soluble polymer for use in this invention containsat least 10 mole percent of a repeating monomer unit represented by thestructure: ##STR31## wherein R is H or --CH₃

A is --O-- or --N(R₁)--

B is --CH₂ --, ##STR32## and wherein D is ##STR33## and wherein q, m, n,R₁, R₂, R₃, R₄, R₅ and Z have the same meaning as above.

The water-soluble polymers of our invention may be homopolymers or theymay be copolymers, but if they are copolymers, they must contain atleast 2 mole percent of the monomers described above, preferably 10 molepercent of the monomers described above, and most preferably at least 50mole percent of the monomers described above.

When the water-soluble polymers of this invention contain other monomersto form copolymers, terpolymers and the like, the polymers mayadditionally contain vinyl monomers chosen from the group consisting ofacrylamide, methacrylamide, N-methylacrylamide, andN,N-dimethylacrylamide, acrylonitrile, acrylic acid, methacrylic acid,vinyl sulfonate, AMPS¹, vinyl acetate, DADMAC², MAPTAC³, DMAPMA⁴, DMAEM⁵and its quaternary salts, DMAEA⁶ and its quaternary salts, ethylacrylate, methyl acrylate, N-vinyl pyrrolidone, or any mixtures thereof.

The water-soluble polymers may contain active hydrogen functionalitysince this functionality can be reactive with the aldehyde andhemiacetals which are present in the monomers used to form thewater-soluble polymers of this invention and under appropriateconditions can cause crosslinking or thermosetting properties. However,these crosslinking reactions can be controlled by the original formationof a water-soluble polymer in the acetal form which, when applied topaper, is hydrolyzed in situ forming the hemiacetal or aquated aldehydewhich then subsequently combines with cellulosic fibers leading to theimproved paper strength properties found in this invention.

The preferred water-soluble polymers of this invention are thosepolymers which are copolymers with cationically charged monomers. Thesecationically charged monomers may be chosen from the group consisting ofMAPTAC, DADMAC, DMAEM and its quaternary salts, DMAEA and its quaternarysalts, and/or monomers represented by the structure: ##STR34## wherein Ris --H, --CH₃, or C₂ H₅, and A=--O--, or ##STR35## and wherein R₁, R₂,and R₃ may be the same or different and are --H, --CH₃, --C₂ H₅, or (Ch₂CH₂ O)_(q) H; q is between 1-6; and Z is Cl, Br, and I, and mixturesthereof.

Although we have listed several cationic monomers which form copolymerswith the monomers of this invention, other cationic monomers which arecapable of free radical vinyl polymerization may also be used and aremeant to be included in this invention.

The water-soluble polymers of this invention may also include copolymerswith anionic monomers. Such anionic monomers may be chosen from thegroup consisting of acrylic acid, methacrylic acid, maleic anhydride,vinyl sulfonate, AMPS, sulfonated styrene, and monomers represented bythe structure: ##STR36## wherein R=H, CH₃, or C₂ H₅

A=--O-- or --N(R)--

M=H, Na, Li, K, Mg, Ca, and the like, and

q is between 1-6.

and mixtures thereof.

In addition, the polymers of this invention may include copolymers withneutral water-soluble monomers or copolymers of a neutral characterwhich when polymerized with the monomers of this invention, formwater-soluble polymers. These neutral monomers may be chosen from thegroup consisting of acrylamide, methacrylamide, N-substitutedacrylamides or methacrylamides, ethoxylated acrylamides, N-vinylpyrrollidone, ethyl acrylate, methyl acrylate, vinyl acetate, andmixtures thereof.

Finally, the copolymers of this invention may contain more than 2monomers, either chosen from preferred structures of the monomers ofthis invention or chosen from any of the listed monomers above. Forexample, terpolymers of acrylamide, the preferred monomers above, andDADMAC may be easily synthesized and used to improve strengthcharacteristics in paper sheet when combined with the cellulosic fibersmaking up the paper sheet.

The water-soluble polymers of this invention must have a molecularweight of at least 1,000, and preferably they have a molecular weight ofat least 5,000. When certain monomers are used in combination with themonomers of this invention, the water-soluble polymers of this inventionmay have molecular weights exceeding 1,000,000.

The polymers of this invention may also be made by chemical adduction ofreactive compounds onto the backbone of existing polymeric species. Forexample, vinyl polymers having appropriate reactive substituents and thechemicals described above may be reacted to accomplish a chemicaladduction to yield homopolymers or the co- and/or ter-polymers of thisinvention.

For example a polyacrylonitrile may be dispersed or dissolved in anappropriate reaction media: then reacted with anhydrous ferric chlorideand the reactant R'₄, where

Z=Cl, Br, I and the like,

and where

R'= ##STR37## and where R₃ = ##STR38## R₄ and R₅ are the same ordifferent and may, at each individual occurence, be H, --CH₃, --C₂ H₅and the like, and n=1-6.

This adducted polymer is then reacted with water to yield a polymer ofthis invention. Similarly cationically modified acrylamide or copolymersor acrylamide containing amino substitution may be quaternized with thereactant R'Z above to yield the polymers of this invention, i.e.:

A polymer represented by: ##STR39## may be reacted with the reactant R'Zabove to achieve the copolymer of the invention. In this example, if xis zero, and the chemical adduction is complete, a homopolymer would beexpected, if x and y are both not zero, and the adduction reaction withR'Z is complete, a copolymer would be expected, and if x is zero, andthe adduction is incomplete a copolymer is expected, or if x and y areboth not zero and the adduction reaction is not complete, a terpolymeris expected.

Finally, polymers of this invention may be manufactured by reactingdispersed or dissolved polymer, in an appropriate solvent, in thefollowing reaction sequence: ##STR40## wherein R may be H, CH₃, C₂ H₅and the like; and R₁ may be same or different as R, and y and x arenormally greater than 10, but y may be zero, and B, q, R₄ and R₅ havetheir previous meaning.

Paper Compositions

The paper compositions of this invention comprise cellulosic fiberscombined with a water-soluble polymer which contains at least 2 molepercent of a monomer represented by the chemical structure: ##STR41##wherein R is --H, --CH₃, or --C₂ H₅ ; and

A is O, or N(R₁); and

B is CH₂, CH₂ CH₂ O, ##STR42## and D is ##STR43## and wherein R₁ is --H,--CH₃, --C₂ H₅, (CH₂ CH₂ O)_(n) H, or (B)_(q) D, and wherein q is from1-6, except when B contains nitrogen in which case q is always one; andwherein R₂ is --H, --CH₃, --C₂ H₅, or (CH₂ CH₂ O)_(n) H; and wherein R₃is ##STR44## and wherein R₄ and R₅ may be the same or different and are,for each individual occurance, --H, --CH₃, or --C₂ H₅ ; and wherein Z isfrom the group Cl, Br, I, NO₃, SO₄ and the like; and wherein m rangesfrom 0-6; and wherein n is from 1-6.

Again, the cyclic acetals which are assymetrically substituted areincluded in these definitions.

The word "paper" is herein used to include any cellulose containing mator web which is prepared by screening a dilute cellulose fibersuspension, which may or may not contain other fibrous matter such asrayon, nylon, glass fiber and the like, in water. Examples of thisinclude:

Non-woven fabrics

roofing felt

molded products (e.g. egg cartons)

ceiling tile

The paper compositions above may contain the cellulosic fibers and thewater-soluble polymers described above dispersed one within the othersuch that no significant concentration gradient of polymer exists withinthe paper sheet. This is usually accomplished by admixing thewater-soluble polymers of this invention with the cellulosic fibersprior to paper sheet formation. However, this may also be accomplishedby adding solutions of the water-soluble polymers described above to apreformed sheet and then drying.

The paper compositions may also contain the water-soluble polymercombined with only the surface cellulosic fibers on the surfaces of thepaper sheet. This is most likely accomplished by spraying the solutionsof the polymer onto a preformed paper sheet or applying solutions of thepolymer to the paper sheet using draw down knives, brushes, low pressuresprays, and such other application techniques. It is preferred that thepaper composition comprise cellulosic fibers combined with thewater-soluble polymers described above such that no concentrationgradient of the polymer exists within the paper.

Test procedures used to define wet strength, dry strength, and the likeare found in TAPPI Official Test Method T 494 om-81 and is a TAPPIOfficial Test Method published in 1981. This method allows tensilebreaking properties of paper and paperboard using constant rate ofelongation apparatus to be properly measured. The test referred to aboveis a TAPPI test for dry strength. We have modified this test to test wetstrength in the following manner: a paper sheet cut to appropriatedimensions is inserted into the test apparatus. A camelhair brush isused to wet the test strip in its center while the sample is in the jawsof the test equipment. De-ionized water is always used to wet the teststrip. After the water has been applied using the camelhair brush for 10seconds, the test strip is broken in the tester and the wet strengthmeasured thereby. Testing methods for wet web strength are found inScandanavian Pulp, Paper and Board Testing committee SCAN-C 35:81, andSCAN-M 12:81, and R. S. Seth, et al, TAPPI 65 (3) 135 (1982), which isincorporated herein by reference.

To better describe the preparation of the monomers of this invention,the water-soluble polymers of this invention, and their use in formingpaper sheet having improved strength by combining cellulosic fibers withthe water-soluble polymers described above, the following examples arepresented.

EXAMPLES Example 1 Preparation of N-(2,2 dimethoxyethyl)acrylamide

A 3000 ml. round bottom flask was fitted with a mechanical stirrer, adropping funnel, a thermometer, and a dry ice reflux condenser. To theflask was charged 271.9 grams of aminoacetaldehyde dimethylacetaldissolved in 1295 ml. of ethyl ether. To the dropping funnel was charged117.0 grams of acryloylchloride dissolved in 430 ml. of ethyl ether.

The round bottom flask was suspended in a dry ice-isopropanol bath. Whenthe contents reached 0° C., the acryloylchloride solution was allowed toslowly drip into the flask. Temperature was maintained at 0° to 3° C.over a 40 minute period during which all the acryloylchloride solutionhad been added. Voluminous white crystals of aminoacetaldehydedimethylacetal hydrochloride were present in the product. These crystalswere removed via filtration. Methoxyhydroquinone (0.1 gram) was addedand the filtrate was concentrated by evaporation of the ethyl ether toyield 189 grams of N-(2,2 dimethoxyethyl)acrylamide (92% yield).

Example 2 Preparation of N-methyl, N-(2,2 dimethoxyethyl)acrylamide

This monomer was prepared in a manner similar to that of Example 1.Charged to the flask was 300 grams of methylaminoacetaldehydedimethylacetal dissolved in 1300 ml. of ethyl ether. Charged to thedropping funnel was 114 grams of acryloyl chloride dissolved in 420 ml.of ethyl ether. The acryloyl chloride solution was added during a 35minute period while maintaining -10° to -5° C. The slurry of aminehydrochloride that formed was very viscous. An additional 350 ml. ofethyl ether was added to minimize this.

Isolation of the product was as described in Example 1. Yield was 161grams (74%).

Example 3 Preparation of 2,2 diethoxyethyl-methacrylate

A one liter round bottom flask was equipped with a mechanical stirrer,thermometer, and reflux condenser. Charged initially to the flask were210.5 grams of triethylamine followed by 179.0 grams of methacrylicacid. A water bath was used to keep the temperature near ambient duringthis step.

When all the methacrylic acid had been charged, 410.0 grams ofbromoacetaldehyde diethylacetal was added. This mixture was then heatedto reflux (approximately 123° C.) for a period of 38 hours. During thisperiod the temperature ranged between 123° and 138° C. White crystals oftriethylamine hydrobromide formed in the solution and at one pointsublimed into the condenser.

The crystals were filtered and washed with 300 ml. of ethyl ether. Thesefiltrates were combined and washed with two 1000 ml. portions of watercontaining a small amount of sodium sulfate. Additional quantities ofethyl ether (total of 500 ml.) were added to effect a reasonably goodseparation of the phases in a separatory funnel.

The ether solution of the product was dried with 150 grams of anhydrouspotassium carbonate. After removal of the ethyl ether via distillation,the product was fractionally distilled to yield:

#1. 15.2 grams (b.p.=23°-62° C./16 mm.)

#2. 56.9 grams (b.p.=71°-90° C./16 mm.)

#3. 124.0 grams (b.p.=94°-108° C./16 mm.)

Analysis indicated that fraction #1 was predominantly ethylmethacrylate. Fraction #2 was predominantly bromoacetaldehydediethylacetal. Fraction #3 was the desired product, 2,2diethoxy-ethyl-methacrylate (29% yield).

Examples 4 and 5 Preparation of:

(a) N-(2-hydroxy, 2-methoxyethyl)acrylamide;

(b) N-(2,2 dihydroxyethyl)acrylamide;

(c) N-methyl, N-(2-hydroxy, 2-methoxyethyl)acrylamide;

(d) N-methyl, N-(2,2 dihydroxyethyl)acrylamide.

These monomers were prepared by the acid hydrolysis of the monomersdescribed in Examples #1 and #2. The experiments were carried out in NMRtubes and the spectra proved the structures to be the compounds soughtto be synthesized.

Example 6 Preparation of the copolymer of N-(2,2dimethoxyethyl)acrylamide with methacrylamidopropyl trimethyl ammoniumchloride

Combined in a 50 ml. beaker on a magnetic stir plate was:

15.1 grams of the monomer described in Example #1;

2.2 grams of a 50% aqueous solution of methacrylamidopropyl trimethylammonium chloride;

14.54 grams water;

0.05 grams ammonium persulfate.

To this solution was added 0.11 grams of sodium meta bisulfite dissolvedin 4.0 grams of water. Upon addition of the sodium metabisulfitesolution the mixture exothermed from 26° C. to 77° C. during a fourminute period. The viscous polymer solution that resulted was determinedto be of molecular weight approximately equal to 37,000.

Example 7 Preparation of the terpolymer of N-(2,2dimethoxyethyl)acrylamide; acrylamide; and dimethyl-diallyl-ammoniumchloride

Charged to a Dewar flask equipped with a thermometer and mechanicalstirrer were the following:

10.2 grams of a 49% aqueous dimethyl-diallylammonium chloride solution

52.6 grams of a 42.8% aqueous solution of acrylamide

102.2 grams of a 50% aqueous solution of N-(2,2dimethoxyethyl)acrylamide

75.9 grams of water

The mixture was adjusted to pH=8.5 with sodium hydroxide. There was thenadded in rapid succession:

a solution of 0.167 grams of ammonium persulfate in 5.0 grams of water.

a solution of 0.333 grams of sodium metabisulfite dissolved in 5.0 gramsof water.

Upon addition of the last ingredient the reaction mixture exothermedfrom 21.5° C. to 71.8° C. during a six minute period.

The viscous solution that resulted was determined to contain polymer ofmolecular weight approximately equal to 55,000.

                                      TABLE I                                     __________________________________________________________________________                                                  % by weight of a                                                              2/1, (w/w, sodium-                                              Polymer Con-                                                                          Polymer                                                                             metabisulfite/                  Example                 Monomer Ratio                                                                         centration                                                                            Molecular                                                                           ammonium persulfate             Number                                                                             Polymer Composition                                                                              (w/w)   in water                                                                              Weight                                                                              initiator                       __________________________________________________________________________                                                  (BOM)                            #8  N--(2,2 dimethoxyethyl) acrylamide/                                                              95.3/4.7                                                                              42.3%   35,000                                                                              0.47%                                dimethyl-diallyl-ammonium chloride                                        #9  N--(2,2 dimethoxyethyl) acrylamide/                                                              64.7/28.9/6.4                                                                         31.2%   2,500,000                                                                           Initiator was 0.0963%                acrylamide/dimethyl-diallyl-ammonium     ammonium persulfate;                 chloride                                 0.0032% ferrous                                                               ammonium sulfate                                                              (.6H.sub.2 O); 0.0096%                                                        sodium bisulfite (all                                                         BOM).                           #10  N--(2,2 dimethoxyethyl) acrylamide                                                               100     44.8%   41,000                                                                              0.56%                           #11  N--methyl, N--(2,2 dimethoxyethyl)                                                               66.6/27.3/6.1                                                                         32.8%   350,000                                                                             0.76%                                acrylamide/acrylamide/dimethyl-                                               diallyl-ammonium chloride                                                #12  N--methyl, N--(2,2 dimethoxyethyl)                                                               95.6/4.4                                                                              44.7%   96,000                                                                              0.55%                                acrylamide/dimethyl-diallyl-                                                  ammonium chloride                                                        __________________________________________________________________________

Example 13 Polymerization of 2,2 diethoxyethyl methacrylate

The monomer of Example #3 was polymerized as follows: A 250 ml., threeneck flask was equipped with a stirrer, thermometer, nitrogen inlet, andnitrogen outlet. Charged to the flask were:

92.75 grams of water

1.25 grams disodium hydrogen phosphate

6.00 grams Triton X-200 (Rohm & Haas)

50.00 grams 2,2 diethoxyethyl methacrylate

This mixture was adjusted to pH=7.5 with hydrochloric acid. Thefollowing were then added:

1.00 grams of a 0.15% aqueous solution of ferrous sulfate (0.7H₂ O)

0.25 gram of ammonium persulfate

2 drops of tert-butyl hydroperoxide (70%)

0.25 gram of sodium meta-bisulfite

During this period of time the reaction mixture exothermed from 21° C.to 46° C. The final product was a white latex polymer which containedapproximately 11 grams of coagulum which was separated and discarded.Evaporation of the water in a portion of the finished polymer left aclear flexible residue equal to 33% of the initial weight.

Example 14 Hydrolysis of the polymer of Example 8

The following mixture was prepared:

25 grams of a 42.3% aqueous solution of the copolymer of N-(2,2dimethoxyethyl)acrylamide with dimethyl-diallyl-ammonium chloride (seeExample #8)

50 grams of 0.5 normal hydrochloric acid

25 grams of water

This mixture was placed in a bottle and immersed in a 30.0° C. waterbath. The hydrolysis of the acetal groups in the polymer to yield bothhemiacetal and hydrated aldehyde groups was followed with time bywithdrawing aliquotes of the reaction mixture and titrating them. Thetitration procedure was a modification of that of Bryant (J. Am. Chem.Soc., Vol. 57, p. 57ff, 1935). The modifications consists of:

(a) Use of anhydrous solvents for reagent preparation (thus allowinglarger introduction of water with the samples).

(b) Incorporating a "pre-titration" of the acidity of the sample due tothe use of hydrochloric acid to promote hydrolysis. This is done priorto the introduction of the pyridine or hydroxylamine hydrochloridereagents.

(c) Incorporating a reaction period of 20 minutes at 70° C. for reactionof the hydroxylamine hydrochloride with the sample.

(d) Use of a filtration step prior to the final titration when necessaryto remove generated solids. From another experiment (see NMR/titrationresults), it has been determined that a "conversion" thus determined isthe sum of hemiacetal and hydrated aldehyde groups.

Using the above procedures, the following data was generated during theabove hydrolysis experiment.

                  TABLE II                                                        ______________________________________                                                  Meq. of Acidity                                                               per gram of  Meq./gram                                              Elapsed   sample       (final     Acetal                                      Time      (pre-titration)                                                                            titration) Conversion                                  ______________________________________                                        0 hour    0.244        0.000       0%                                         1 hour    0.243        0.166      26%                                         21/2 hours                                                                              0.242        0.332      52%                                         32/3 hours                                                                              0.242        0.434      68%                                         22 hours  0.242        0.556      88%                                         ______________________________________                                    

The 22 hour sample showed some signs of gellation. This gel was,however, reversible through further dilution with water.

Example 15 Hydrolysis of the polymer of Example 7

An experiment similar to that cited in Example #14 was carried out usingthe terpolymer of Example #7. Hydrolysis mixture:

25.0 grams of the polymer solution of Example #7;

50.0 grams of 0.5 normal hydrochloric acid;

25.0 grams of water.

                  TABLE III                                                       ______________________________________                                                  Meq./gram                                                           Elapsed   Acidity      Meq./gram  % Acetal                                    Time      (pretitration)                                                                             (Final)    Conversion                                  ______________________________________                                        0 hour    0.242        0.000       0%                                         1 hour    0.244        0.080      25%                                         21/2 hours                                                                              0.245        0.151      48%                                         32/3 hours                                                                              0.243        0.186      59%                                         21 hours  0.239        0.257      81%                                         ______________________________________                                    

Examples 16 to 19

These hydrolysis experiments were carried out in a fashion similar toExamples #14 and #15:

                  TABLE IV                                                        ______________________________________                                        Example    Starting Polymer                                                                            Conversion Range                                     ______________________________________                                        #16        Example #9    0-30%                                                #17        Example #11   0-75%                                                #18        Example #12   0-77%                                                #19        Example #10   0-approx. 80%                                        ______________________________________                                    

Example 20 Cationization of the hydrolyzed homopolymer of N-(2,2dimethoxyethyl)acrylamide and preparation of a paper composition

The following mixture was prepared:

10.64 grams of a hydrolyzed 10% solution of poly-N(2,2dimethoxyethyl)acrylamide (see Example #19);

10.00 grams of a 10% solution of sodium acetate (0.3H₂ O);

169.36 grams of water;

10.00 grams of an aqueous 0.564% solution of Girard's reagent T.

The pH of this solution was adjusted to 6.0 with sodium hydroxide. Adilute paper fiber slurry was treated with this solution within 1 hourof preparation of the solution. Handsheets prepared from this slurry hadmuch improved wet and dry strength properties as compared to untreatednandsheets, indicating a high retention (and successful cationization)of the polymer product. The handsheets were prepared in a semi-automaticBritish sheet mold from a 50/50 mixture of bleached hardwoodkraft/bleached softwood kraft paper fiber. Sheet forming pH was 6.0. Theresults are shown in Table V.

                  TABLE V                                                         ______________________________________                                                   Treatment Dry Tensile  Wet Tensile                                 Sample     Level*    (lb./inch)   (lb./inch)                                  ______________________________________                                        Blank      0%        37.4          1.875                                      Cationized 0.25%     47.4         11.650                                      Polymer                                                                       Cationized 0.50%     52.1         17.700                                      Polymer                                                                       Cationized 0.75%     56.8         20.040                                      Polymer                                                                       Parez 631NC**                                                                            0.75%     50.9         15.730                                      ______________________________________                                         *Treatment level is % based on fiber of the poly N--(2,2 dimethoxyethyl)      acrylamide hydrolysis product. For Parez 631NC, it is active solids as        defined by its manufacturer.                                                  **Parez 631NC is a commercial wet strength product manufactured by            American Cyanamid. Believed to be a copolymer of 95 parts by weight           acrylamide with 5 parts of dimethyldiallyl-ammonium chloride. This            copolymer is then reacted with up to 30 parts (by weight) of glyoxal.    

EXAMPLE 21 Preparation of a paper composition containing hydrolyzed andcationized poly-N-(2,2-dimethoxyethyl)acrylamide

The hydrolyzed and cationized polymer solution described in Example #20was used to saturate samples of Whatman No. 1 filter paper. Thesaturated paper samples were dried in a 215° F. oven for 10 minutes.Through paper dilution of the saturating solutions, a range of treatmentlevels was obtained. Solution pH's were maintained at 6.0. The resultsare shown in Table VI.

                  TABLE VI                                                        ______________________________________                                                     Treatment Dry Tensile                                                                              Wet Tensile                                 Sample       Level*    (lb./inch) (lb./inch)                                  ______________________________________                                        Blank        0%        12.8       0.700                                       Cationized   0.25%     15.1       3.910                                       Polymer                                                                       Cationized   0.50%     16.9       5.083                                       Polymer                                                                       Cationized   0.75%     18.1       7.600                                       Polymer                                                                       Parez 631NC**                                                                              0.75%     16.8       4.353                                       ______________________________________                                         *See Example #20.                                                             **See Example #20.                                                       

EXAMPLE 22 Preparation of paper compositions containing hydrolyzedpolymers of differing conversions

The following materials were charged to a bottle which was then placedin a 30.0° C. watch bath during the hydrolysis period:

25 grams of the polymer solution of Example #7;

25 grams of water;

50 grams of 0.5 normal hydrochloric acid.

At the times indicated, samples were withdrawn and titrated to determineextent of conversion. Separate samples were withdrawn and diluted asfollows:

6.88 grams of sample from the above mixture;

5.00 grams of a 10% NaC₂ H₃ O₂.3H₂ O solution (buffer);

88.12 grams of water.

These solutions were adjusted to pH=6.0 with sodium hydroxide. Samplesof Whatman No. 1 filter paper were immediately saturated and dryed asdescribed in Example #21. This procedure resulted in 0.75% by weight ofthe polymer being applied to the paper. The results of this testing areset forth in Table VII.

                  TABLE VII                                                       ______________________________________                                        Elapsed  % Acetal    Dry Tensile                                                                              Wet Tensile                                   Time     Conversion  (lb./inch) (lb./inch)                                    ______________________________________                                        0 minutes                                                                               0%         4.09       0.24                                          100 minutes                                                                            33%         5.33       1.19                                          210 minutes                                                                            71%         6.12       1.60                                          405 minutes                                                                            73%         6.10       1.59                                          1350 minutes                                                                           87%         6.28       1.89                                          blank    --          4.70       0.28                                          ______________________________________                                    

EXAMPLE 23 Performance of papers prepared on a semi-automatic Britishsheet mold

                  TABLE VIII                                                      ______________________________________                                               Wet Web   Rewetted    Dry                                                     Strength  Strength    Strength                                                  Dose   Dose     Dose Dose   Dose Dose                                Sample   1%     5%       1%   5%     1%   5%                                  ______________________________________                                        Blank    232    209       259  297   4291 4054                                Sample A*                                                                              414    626      2431 3605   4490 4491                                Sample B*                                                                              356    288      2685 2700   4495 4457                                Sample C*                                                                              449    358      3288 2918   4423 4504                                Sample D*                                                                              503    807      2572 3607   4521 4537                                ______________________________________                                         *Sample A = The polymer of Example #16                                        *Sample B = The polymer of Example #14                                        *Sample C = The polymer of Example #15                                        *Sample D = a glyoxalated acrylamide/DADMAC copolymer.                        Note:                                                                         1. All results are grams/inch peak load.                                      2. All product dosages are expressed as equivalent to a 90/10 (w/w),          acrylamide/DADMAC backbone (% based on dry fiber).                            3. Sheet solids for wet web results is approximately 30-35%.                  4. Stock is 92% repulped stock (40% stone groundwood, 40% bleached kraft,     20% TMP) and 8% bleached kraft. Sheets were formed in deionized water at      natural pH (approximately 5.7).                                          

EXAMPLE 24

A solution was prepared from the following in a two liter round bottomflask:

477.5 gram 2-methyl 2,4 pentanediol

230.6 gram acrolein (97%)

528.3 gram methylene chloride

The flask was then fitted with a mechanical stirrer, gas inlet tube,therometer, and dry ice condensor. The flask as immersed in a dryice/isopropanol bath and cooled to -10° C. At this time anhydroushydrogen chloride gas was bubbled into the solution until no more gaswas absorbed. Temperature was maintained at approximately -10° C.throughout this process.

After the gas absorbtion was complete the material was warmed to ambienttemperature and the bottom aqueous layer separated and discarded.Following this, the organic layer was washed with water, neutralizedwith a sodium bicarbonate solution and dried over magnesium sulfate. Thefiltered product was relieved of methylene chloride by distillation. Theproduct was 793.5 grams of 2-(2-chloroethyl)-4,4,6-trimethyl-1,3dioxane: ##STR45## The following solution was prepared in a bench topautoclave: 84.7 gram product I. (above)

84.7 gram methanol

74.8 gram dimethylaminopropyl methacryalmide

The autoclave was sealed and heated to 100°-110° C. for a period ofapproximately six hours. NMR spectral examination of the final methanolsolution indicated an approximate 80% conversion to: ##STR46##

The following is a list of potential reactants which would give monomersdescribed in Table IX if reacted together according to the previousteachings above.

1. Reactant A (a vinyl containing moiety): ##STR47## where Z=Cl, Br, I

2. Reactant B (an acetal containing moiety):

    H--A--(B)q--D

3. Reactant C (a vinyl containing moiety): ##STR48##

4. Reactant D (an acetal containing moiety):

    X--(CH.sub.2).sub.m --D

If the monomers shown in Table IX where combined with themselves or withany of the above mentioned comonomers, the water-soluble polymers ofthis invention would be expected to form. If these water-solublepolymers were then reacted with a cellulosic substrate a papercomposition of this invention would be expected to form.

                                      TABLE IX                                    __________________________________________________________________________    Reactant                                                                      Combination                                                                          R    A   B            q  D           n R.sub.1                         __________________________________________________________________________    A + B  C.sub.2 H.sub.5                                                                     ##STR49##                                                                        CH.sub.2     1  CH(OCH.sub.3).sub.2                                                                       --                                                                              H                               A + B  H                                                                                   ##STR50##                                                                        CH.sub.2     2  CH(OCH.sub.3).sub.2                                                                       --                                                                              H                               A + B  H                                                                                   ##STR51##                                                                        CH.sub.2     6                                                                                 ##STR52##  --                                                                              (CH.sub.2 CH.sub.2 O).sub.m                                                   H                               A + B  H                                                                                   ##STR53##                                                                        CH.sub.2     2  CH.sub.2CH(OCH.sub.3).sub.2                                                                 (B).sub.qD                      C + D  CH.sub.3                                                                           O                                                                                  ##STR54##   1  CH.sub.2CH(OCH.sub.3).sub.2                                                               2 CH.sub.3                        A + B  H    O   CH.sub.2 CH.sub.2 O                                                                        1-6                                                                              CH.sub.2 CH(OCH.sub.3).sub.2                                                              --                                                                              --                              A + B  H                                                                                   ##STR55##                                                                        CH.sub.2     2  (CH.sub.2).sub.0-6 CH(OCH.sub.3).sub.2                                                    --                                                                              C.sub.2 H.sub.5                 C + D  H    O                                                                                  ##STR56##   1  CH.sub.2CH(OCH.sub.3).sub.2                                                               2 CH.sub.3                        C + D  H    NH                                                                                 ##STR57##   1  CH(OCH.sub.3).sub.2                                                                       Z CH.sub.3                        __________________________________________________________________________    Reactant                                                                      Combination                                                                          R.sub.2 Z   m   Monomer Produced                                       __________________________________________________________________________    A + B  --      --  --                                                                                 ##STR58##                                             A + B  --      --  --                                                                                 ##STR59##                                             A + B  --      --  2                                                                                  ##STR60##                                             A + B  --      --  --                                                                                 ##STR61##                                             C + D  CH.sub.3                                                                              Br  1-6                                                                                ##STR62##                                             A +  B --      --  --                                                                                 ##STR63##                                             A + B  --      --  0                                                                                  ##STR64##                                             C + D  C.sub.2 H.sub.5                                                                       I   1                                                                                  ##STR65##                                             C + D  CH.sub.2 CH.sub.2 OH                                                                  Cl  2                                                                                  ##STR66##                                             __________________________________________________________________________

As can be seen from the data presented above, the water-soluble polymersof this instant invention are readily formed from the monomers of thisinvention. These monomers are capable of polymerization to give stableproducts of linear polymers of relatively high molecular weight. It isimportant that the acetal functionality be hydrolyzed to form thehemiacetal or free aldehyde functionality to obtain the strengthproperties above. To do so, the method of Bryant, which is incorporatedherein by reference, as published in the Journal of the AmericanChemical Society in 1935, was adapted to follow the acetal hydrolysis ofthe products of this invention.

In addition, Nuclear Magnetic Resonance experiments were used to followthe acetal hydrolysis. These results confirm the anticipated structureof the polyacetal materials and have not detected any amide hydrolysiswhich may be simultaneously competitive with the acetal hydrolysis. Inaddition, the Nuclear Magnetic Resonance studies referred to abovesuggest that both hemiacetal and hydrated aldehydes are produced whenthe acetal structures are hydrolyzed. Our work seems to indicate thatboth hemiacetal as well as hydrated aldehyde structures are reactivewhen combined with cellulosic fibers and do form paper compositionshaving improved paper strength properties. However, it would seemapparent from the results above that the degree of acetal hydrolysisrelates to the performance of the hydrolyzed polymers as a paperstrengthening agent. Therefore, high conversion of acetal to hemiacetaland hydrated aldehyde is very desirable.

The data presented above also indicates that a dose performanceimprovement is observed when the polymers of the instant invention arecompared with the polymers commercially available under the teachings ofU.S. Pat. No. 3,556,932, previously incorporated herein by reference.

Having described our inventions, we claim:
 1. A water-soluble polymerwhich contains at least two mole percent of a monomer unit representedby the chemical structure: ##STR67## wherein R is H, CH₃, or C₂ H₅ ;andA is O, or N(R₁); and B is CH₂, CH₂ CH₂ O, ##STR68## and D is##STR69## and wherein R₁ is H, CH₃, C₂ H₅, (CH₂ CH₂ O)_(n) H, or (B)_(q)D, and wherein q is from 1-6, except when B contains nitrogen in whichcase q is always one; and wherein R₂ is H, CH₃, C₂ H₅, or (CH₂ CH₂O)_(n) H; and wherein R₄ and R₅ may be the same or different and are,for each individual occurrence, H, CH₃, or C₂ H₅ ; and wherein Z is fromthe group Cl, Br, I, NO₃, or SO₄ ; and wherein m ranges from 0-6; andwherein n is from 1-6.
 2. The water-soluble polymer of claim 1containing at least ten mole percent of a monomer unit represented bythe structure: ##STR70## wherein R is H, or CH₃,A is O or N(R₁) B isCH₂, ##STR71## and wherein D is ##STR72## and wherein q, m, n, R₁, R₂,R₄, R₅, or Z have the same meaning as in claim
 1. 3. The water-solublepolymer of claim 1 wherein the polymer additionally contains a monomerunit chosen from the group consisting of acrylamide, methacrylamide,acrylonitrile acrylic acid, methacrylic acid, vinyl sulfonate,acrylamidopropane sulfonic acid, vinyl acetate, dially dimethyl ammoniumchloride, methacrylaminopropyl trimethyl ammonium chloride,dimethylaminopropyl methacrylate, dimethyl amino ethyl methacrylate, andits quaternary salt, dimethyl amino ethyl acrylate and its quaternarysalt, N-vinyl pyrollidone, ethyl acrylate, and methyl acrylate.
 4. Thewater-soluble polymer of claim 2 wherein the polymer contains at least10 but less than 98 mole percent of a monomer unit chosen from the groupconsisting of acrylamide, methacrylamide, acrylonitrile acrylic acid,methacrylic acid, vinyl sulfonate, N-vinyl pyrollidone,acrylamidopropane sulfonic acid, diallyl dimethyl ammonium chloride,methacrylamidopropyl trimethyl ammonium chloride, acrylamide,ethylacrylate, methylacrylate, and vinyl acetate.
 5. The water-solublepolymer of claim 1 wherein the polymer is a homopolymer with a monomerunit represented by the structure: ##STR73## wherein R is H, CH₃, or C₂H₅ ; andA is O, or N(R₁); and B is CH₂, CH₂ CH₂ O, or (CH₂ --_(n)N(R₁)--CH₂)_(m), ##STR74## and D is ##STR75## and wherein R₁ is H, CH₃,C₂ H₅, (CH₂ CH₂ O)_(n) or (B)_(q) D, and wherein q is from 1-6, exceptwhen B contains nitrogen in which case q is always one; and wherein R₂is H, CH₃, C₂ H₅, or (CH₂ CH₂ O)_(n) H; and wherein R₄ and R₅ may be thesame or different and are, for each individual occurrence, H, CH₃ or C₂H₅ ; and wherein Z is Cl, Br, I, NO₃, or SO₄ ; and wherein m ranges from0-6; and wherein n is from 1-6.
 6. The water-soluble polymer of claim 1wherein the polymer is a copolymer which includes cationically chargedmonomer units from the group consisting of methacrylamidopropyltrimethyl ammonium chloride, diallyl dimethyl ammonium chloride, ormonomers represented by the structure: ##STR76## wherein R is H, CH₃, orC₂ H₅, and A=O, or ##STR77## and wherein R₁, R₂, and R₃ is H, CH₃, C₂H₅, or (CH₂ CH₂ O--_(q) H; q is between 1-6; and Z is Cl, Br, or I. 7.The water-soluble polymer of claim 1 wherein the polymer is a copolymerwhich includes anionic monomers chosen from the group consisting ofacrylic acid, methacrylic acid, maleic anhydride, vinyl sulfonate,acrylamidopropane sulfonic acid, sulfonated styrene, and monomersrepresented by the structure: ##STR78## wherein R=H, CH₃, or C₂ H₅ A=Oor N(R) M=H, Na, Li, K, Mg, or Ca; and q is between 1-6.
 8. Thewater-soluble polymer of claim 1 wherein the polymer is a copolymerwhich includes neutral monomer units chosen from the group consisting ofacrylamide, methacrylamide, ethoxylated acrylamide, N-vinyl pyrollidone,ethyl acrylate, methyl acrylate, vinyl acetate, and mixtures thereof.